Aminomethylpyrrolidinones



United States Patent O 7 2,984,673 AMINOMETHYLPYRROLEINONES Newman M.Bortnick, Oreland, and Marian F. Fegley, Mont Clare, Pa., assign'ors toRohm & Haas Company, Philadelphia, Pa., a corporation of Delaware 1- NbDrawing. Filed June 18, 1958, Ser. No. 742,735

13 Claims. or. 260-3265) This invention deals with specificaminomethylpyrrolidinones as new compositions of matter. It furtherdeals with a method for the preparation of these specificaminomethylpyrrolidinones.

The present compounds are prepared by hydrogenating specificcyanopyrrolidinones having the formula The symbol R represents ahydrocarbon group of one to ten carbon atoms, preferably alkyl, aralkylcycloalkyl, aryl and alkaryl. The symbol R represents a hydrogen atom oran alkyl group of one to four carbon atoms. The symbols R and R may behydrogen or hydrocarbon groups of one to ten carbon atoms includingalkyl, aralkyl, cycloalkyl, aryl and alkaryl groups. In addi tion, R andR taken together with the carbon atoms to which they are joined may forma carbocyclic ring containing five to six carbon atoms which in turn mayhave .alkyl substituents containing a total of no more than fouradditional car-hon atoms. In addition, R and R taken together with thecarbon atoms to which they are joined may form a carbocyclic ringcontaining five to six carbon atoms which in turn mayhave alkylsubstituents containing a total of no more than four additional carbonatoms. In addition, R and; R taken together with the carbon atom towhich they are joined may form. a carbocyclic ring-containing five tosix carbon atomswhich in turn may have alkyl substituents containing atotal ofno; more than four additional carbon atoms. The total numberofcarbon atoms in the groups R R R and R should not exceed 20. Thepreferred embodiments are those in which R and R are alkyl groups, R isa hydrogen atom, and R is a methyl group. R R and R may typicallyindividually represent methyl, butyl, octyl, benzyl, phenylbutyl,cyclopentyl, cyclohexyl; phenyl, naphthyl, butylphenyl groups, and thelike.

'Ihe symb ol R represents hydrogen, an alkyl group of one to eighteencarbon atoms, an aryl group of up to ten carbonatoms, an aralkyl groupof up toeighteen carbon atoms, an alkarylalkyl group of up to thirtycarbon atoms, an alkoxyalkyl group of three to twenty-four carbon atoms,a hydroxyalkyl group of two to twelve carbon atoms, and analkylaminoalkyll group ofithree to eighteen 2 carbon atoms provided thatthe amino group is a secondary or tertiary structure, that isnon-primary. Alkyl, in the above definition, is to be construed. toinclude cyclo- =alky1 and alkylcycloalkyl within the range of carbonatoms previously set forth.

Typical R represenations are hydrogen, methyl, ethyl, butyl, octyl,decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, butylcyclohexyl,octylcyclohexyl, butylcyclohexylethyl, phenyl, naphthyl, benzyl,phenylethyl, phenylbutyl, phenyldodecyl, methylphenyl, ethylphenyl,butylphenyl, octylphenyl, nonylphenyl, decylphenyl, hexadecyl-phenyl,octadecylphenyl, methylbenzyl, ethylbenzyl, butylbenzyl, octylbenzyl,dodecylbenzyl, butylphenylbutyl, octylphenylethyl, dioctylphenylethyl,dodecylphenyloctyl, methoxyethyl, methoxyp-ropyl, methoxyhexyl,methoxydecyl, methoxyoct-adecyl, ethoxyethyl, ethoxybutyl, ethoxyoctyl,ethoxydodecyl, propoxyethyl, propoxybutyl, propoxyheptyl,propoxytetradecyl, butoxy ethyl, butoxybutyl, butoxyoctyl,b-utoxydodecyl, butoxyoctadecyl, pentoxyethyl, pentoxybutyl,pentoxydecyl, hexoxyethyl, hexoxyhexyl, hexoxydodecyl, hexoxyoctadecyl,heptoxyethyl, heptoxyoctyl, octoxyethyl, octoxybutyl, octoxyoctyl,octoxydodecyl, nonoxypropyl, nonoxyheptyl, nonoxytridecyl, decoxyethyl,decoxyoctyl, undecoxybutyl, dodecoxypropyl, dodecoxydecyl,dodecoxydodecyl, tridecoxyethyl, tetradecoxypropyl, pentadecoxypentyl,hexadecoxybutyl, heptadecoxyethyl, octadecoxyethyl, octadecoxyhexyl,hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl,hydroxydecyl, hydroxydodecyl, ethylaminoethyl, propylaminoethyl,butylaminopropyl, octylaminohexyl, hexylaminooctyl, heptylaminopentyl,octylaminooctyl, nonylaminoethyl, ethylaminononyl, decylaminopropyl,propylaminododecyl, dodecylaminoethyl, dodecylaminopropyl,dodecylaminobutyl, dodecylaminohexyl, N-methyl-N-ethylaminoethyl, N propyl N-ethylaminoethyl, N-butyl-N-pentylarninoethyl,N-octyl-N-hexylaminobutyl, and N-decyLN-butyb aminob-utyl.

Typical cya-nopyrrolidinone reactants include S-cyano-1,3,3,S-tetramethyl-2-pyrrolidinone, 5-cyano-l-butyl-3,3,5- trimethyl 2pyrrolidinone,S-cyano-lcyclohexyl-3,5-dimethyl-3-(2,2-dimethylpropyl)-2-pyrrolidinone,7a-cyanol-benzyl 3,3-pentamethylene-2,3,3a,4,5,6,7,7a-octahydro' indol 2one, S-cyano-l-1auryl-3,3,S-trimethyl-Z-pyrrolidinone, 5cyano-l-octadecyl-4,S-dimethyl-Z-pyrrolidin one, 5 cyanol,3-dimethyl-3,S biS-(LmethyIpropyl)-2- pyrrolidinone,7a-cyano-l-p-tolyl-3,3,6-trimethyl-2,3,3a,4,5,6,7,7a-octahydroindol-Z-one, 5-cyano-l-benzyl-3,3,5-trimethyl-2-pyrrolidinone, S-cyano-1-(2-hydroxyethyl)-3,3,5-trimethyl-2-pyrrolidinone, S-cyano-1-ethoxyethyl-3,3,5-trimethyl-2-pyrrolidinone, 5-cyano-1-(3-dimethylaminopropyl)3,3,S-trimethyl-Z-pyrrolidinone, S-cyano-LB-dimethyl 3,5dihexyl-Z-pyrrolidinone, 5-cyano-3,3,5-trimethyl 2-pyrrolidinone, 5cyano-3,5-dimethyl-3-(2,2-dimethylpropyl)-2-pyrrolidinone,7a-cyano-3,3-pentamethylene-2,3,3a,4,5,6,7,7a-octahydroindol-Z-one,5-cyan0-4, S-dimethyl-Z-pyrrolidinone, 5-cyano-3-methyl-3,5-bis-(2-methylpropyl') -2- pyrrolidinone, 7a-cyano-3,3,6-trimethyl-2,3,3a,4,5,6,7,7a-bctahydroindol-Z-one, and 5-cyano-3-methyl-3,S-dihexyl-Z-pyrrolidinone. These reactants may be preparedacording to our copending application Serial Number 735,107, filed May14, 1958.

The present hydrogenation is carried out in the presence of a catalyst.Suitable as catalysts are Raney nickel, Raney cobalt, cobalt withammonia, nickel with ammonia, cobalt-copper, nickel-cobalt, palladium,platinum, ruthenium, and the like. The catalyst may be employed in anyconvenient particle size. Generally, the smaller particle sizes producethe higher rate. If desired, the catalyst maybe deposited on a. carriermaterial in order to. extend and activate it. Suitable for use as acanrier are activated alumina, activated clays, silica gelgcharcoal,asbestos, pumice, and the like. Room temperatures and somewhat abovemaybe employed when a noble metal is used as the catalyst. When theother materials are employed as catalysts, temperatures .in the range ofabout 75 to 250 C. are employed with about l to 200 C. preferred- It ispreferred that the hydrogenation be carried out at the lowesttemperature at Which reduction can occur within the ranges previouslyset out. An inert, volatile, organic solvent may be desirable, such ashydrocarbons, alcohols, ethers, and the like. The lower alkanols, suchas methanol or ethanol, are particularly suited for this use. When thenoble metals are used as catalysts, a small amount of an activatingacid, such as acetic or hydrochloric, may be employed.

lPressures in the range 'of. atmospheric to 10,000 p.s.i.g. areemployed. Actually, higher pressures may be used ifdesired but in mostinstances, no apparent advantages are achieved for the'extra effortextended. The reaction shown proceeds'a little more rapidly at thehigher pres.- sures but lower pressures may be successfully employedwith some of the catalysts, especially Raney'nickel. The preferred rangeof pressures is atmospheric to 100 p;s.i.g. when noble metal catalystsare employed and 250 to 5000 p.s.i.g." when the transition metalcatalysts are used. J Tliepresent reaction should be concluded as soonas two'moles of hydrogen has reacted. Otherwise, if ,the reaction isconducted for periods of time that are substantially longer than thatrequired for two moles of hydrogen to react, there is some chance thathydrogenolysis of the ring may occur. In some instances, this has beenobserved when the reaction was conducted for prolonged periods of time.While no specific time limit in minutes or hours can be given, sinceactualtimes will vary with cyanopyrrolidinone reactants, catalysts,temperatures, and pressures, it is emphasized that the reaction shouldbe concluded after substantially two moles of hydrogen has reacted.

A preferred way of consummating the is to introduce thecyanopyrrolidinone reactant along with a catalyst of the type describedheretofore into a pressure retention reaction vessel and add hydrogenuntil a certain desired pressure is reached. The reaction vessel or atleast the reaction ingredients may be preferably agitated such as bystirring, rocking, or rotating until a precalculated drop in pressure isobserved. This significant drop in pressure indicates that an equivalentamount of hydrogen has reacted. This precalculated pressure drop,indicating that an equivalent amount of hydrogen has reacted, is readilycalculable by known methods. Therefore, an indication of reactioncompletion may be readily calculated and observed.

At the conclusion of the reaction, the product'is obtained by filteringoff the catalyst and stripping off the solvent. If desired, the productsmay be purified by distillation or recrystallization from hydrocarbons,'ethers, or the like.

The products of this invention are useful as additives for lubricatingoils to minimize and prevent the formation and deposition of sludge, asevaluated by standard methods, in the usual concentrations.

Treatment of these amine products with acid chlorides gives rise toamides which contain the pyrrolidinone function. Acylation of thesimplest members of these series gives rise to amidopyrrolidinones whichhave high solvency for polar polymers, such as polyacrylonitrile andnylon; the N,N-bis-cyanomethyl derivatives thereof likewise function asgood solvents for such polymers. It is possible to treat additionpolymers containing ester groups with these amines and by a process ofdirect aminolysis introduce pyrrolidinone rings into the polymers. Ifthese polymers are fibers, introduction of the pyrrolidinone ringconfers dyeability with acid dyes. 1- hydroxyethyl5-aminomethyl-3,3,S-trimethyl-Z-pyrrolidinone is bifunctional andintroduction of it into condensation polymers prepared from.dicarboxylic acids or diesters present reaction gives polyamido esterscontaining pyrrolidinone rings. Dyeability of fibers containing suchunits is greatly enhanced as compared to simple polyester fibers.Treatment of the aminomethyl compounds with urea leads to substitutedureas. When these are condensed with aldehydes, such as formaldehyde,they become valuable constituents of aminoplastic adhesives and textiletreating materials. The salts of 2,4-dichlorophenoxyacetic acid withthese amines are potent herbicides. The nitrite salts are useful asblowing agents. The latter have the virtue of giving virtually odorlessby-products in the course of the blow. Furthermore, the by-products arecompatible when polyvinyl chloride is thematerial from which the foamsare produced.

The compounds of this invention have been presented in their free-baseform, and in this free-base form they possess the valuablecharacteristics and concurrent utilities previously referred to.However, it isto be; construed that the present invention includes theacidadditionsalts of these free-base products also. It is desirable, insome instances, to employ the present products in their watersolublesalt form. For instance, in pesticidal applications, it is highlydesirable to deal, with water-soluble compounds in order thatsatisfactory spray solutions may be formulated. In other applications,particularly where any physiological benefits are desired, it isfrequent ly advantageous to employ the present products in their organicsalt form in order to provide substantial neutrality with stability.

In order to prepare the salt forms of the present compounds, it isnecessary only to react these compounds with a stoichiometric amount ofthe selected acid. The salt formation occurs readily at room temperature(about 20 C.) without the aid of a catalyst. Temperatures up to about 80C. may be conveniently employed. If solid reactants are employed, it maybe advantageous to use an inert volatile solvent such as benzene,toluene, xylene, hexane, heptane, methylene chloride, chloroform, or thelike. The solvent can then be readily removed at the conclusion of thereaction by conventional methods. The salt product does not requireanyfurther purification although recrystallization from a solvent, suchas isooctane, may be resorted to if a product of high purity isdemanded.

While the method of preparation of the salts is be: lieved to be clearto one skilled in the art from the above description, such saltformation may be specifically illustrated by indicating that one wouldtake anequivalent amount of a selected compound of thisinvention injitsfree-base form and then add a stoichiometric amount of a selected acid,which would, for instance, be 36.5 parts of hydrochloric acid, 98 partsof sulfuric acid, 60 parts of acetic acid, 72- parts of acrylic acid andthe like. The corresponding hydrochloric, sulfuric, acetic and acrylicacid salts respectively are readily formed. Similarly, other saltproducts may be prepared.

Typical organic and inorganic acids that may be employed are fomricacid, acetic acid, propionic acid, butyric acid, caproic acid, capricacid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylicacid, methacrylic acid, crotonic acid, undecylenic acid, oleic acid,linoleic acid, linolenic acid, ricinoleic acid, propiolic acid, butynoicacid, cyclobutane-carboxylic acid, norcamphane-2 carboxylic acid,benzoic acid, resorcylic acid, oxalic acid, succinic acid, glutaricacid, adipic acid, sebacic acid, salicylic acid, maleic acid, fumaricacid, glutaconic, acid, saccharic acid, dodecanedioic acid, octendioicacid, cyclohexaneacetic acid, cyclopentaneacetic acid, tridecanoic acid,hexynedioic acid, phthalic acid, cinnamic acid,,benzenesulfonic acid,ethanesulfonic acid, naphthalenesulfonic acid, toluenesulfinic acid,glutamic acid, glyoxalic acid, phenylglyoxalic, acid, pyruvic acid,levulinic acid,

, glycine, aminocaproic acid, hydrochloric acid, hydrobro- The compoundsof this invention, as well as the. methods for their preparation, may bemore fully understood from the following examples which are offered byway of illustration and not by way of limitation. Parts by weight areused throughout.

Example S-cyano-1,3,3,5-tetrarnethyl-Z-pyrrolidinone (514 parts) absorbshydrogen when heated for one hour at 124-- 134 C. under hydrogen at 2000p.s.i.g. in the presence of Raney nickel catalyst parts). Thereactor iscooled and. vented and the: catalyst is separated by filtration.Distillation of the filtrate gives the product, having a boiling pointof'112-114 C. (2.0. mm), (329 parts) whichcrystallizes in the receiver.The product contains 16.2% nitrogen (theoretical 16.5%) and hasa neutralequivalent of 174 (theoretical 170) The product is identified asS-aminomethyb1,3,3,5-tetramethyl-2-pyrrolidinone.

In. a similar fashion are. prepared 5-aminomethyl-1-butyl-B,3,S-trimethyl-Lpyrrolidinone. from l-butyl-S-cyano-3,3,5-trimethyl-2apyrrolidinone, S-aminomethyl-l-cy- .clohexyl.3,5-dimethyl-3-(2,2-dimethylprop-yl)-2-pyrrolidinone fromS-cyano-l-cyc1ohexyl-3,5-dimethyl-3-(2,2-dimethylpropyl)-2-pyrrolidinone,S-amino-methyl-l-lauryl- 3,3,itrimethyl-Z-pyrollidinone fromS-cyano-l-lauryh 3,3,5 trimethyl 2 pyrrolidinone,5-aminomethyl.-4,5-dimethylpropyl) -2 -pyrrolidinone, S-amino-methyll-laurylmethyl-1-octadecyl-Z-pyrrolidinone, and S-aminomethyl- 1,3dimethyl-3,5-bis-(2 methylpropyl)-2 pyrrolidinone from 5cyano--1,3-dimethyl-3,15abis-(2-nrethylpropyl)-2- pyrrolidinone.Similarly, 5-cyanos3,3,5-trimethyl-2-pyrrolidinone gives5-aminomethyl-3,3,5-trimethyl-2-pyrrolidinone and5-cyano-3,5-dihexyl-1,3-dimethyl-2-pyrrolidinone givesS-aminomethyl-1,3-dimethyl-3,S-dihexyl-Z-pyrrolidinone. The latterexamples are more conveniently carried out when an equal weight ofmethanol is used as a solvent.

Example 2 5 cyano- 1-(2-hydroxyethyl)-3,3,5-trimethyl-2-pyrroli- .dinone(520 parts) and. Raney nickel catalyst, (20 parts) are charged to. areactor and pressurized with hydrogen at 15 00rp.s.i.g. The theoreticalamount of hydrogen is absorbed at 135 -141 C. in the course of two hoursin the shaking autoclave. The bomb is cooled and vented and the.catalyst is separated by filtration. "The filtrate is distilled to givethe product, having a boiling point of 147150 C. (0.5 mm.) (330 parts).The product has 12 value of' 1.4966 and solidifies on standing at roomtemperature overnight in the receiver. The 'prod- Example 3 There areadded to a reaction vessel 8 parts of mesitilonitrile dissolved in 35parts of methanol and 5 parts of 1. Ajr'nembe'n from theclass consistingof the compound having theformul'a and the acid addition salts thereof,in which R; taken individually represents a member from the classconsisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, andalkylphenyl of up to 10 carbon. atoms, R taken individualy represents amember from the class consisting of hydrogen and alkyl of l to 4 carbonatomsgR and R taken individually represent members from the classconsisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl,naphthyl, and alkylpheny of up to 10 carbon atoms, R and R takencollectively with the carbon atoms to which they are joined form amember from the class consisting of a carbocyclic ring of 5 to 6 carbonatoms and said ring having alkyl substituents consisting of a total ofup to 4 carbon atoms, R and R taken collectively with the carbon atomsto which they are joined form a member from the class consisting of acarbocyclic ring of 5 to 6 carbon atoms. and said ring having alkylsubstituents consisting of a total of up to 4 carbon atoms, R andR takencollectively with the carbon atoms to which they are joined form amember from the class consisting of a carbocyclic ring of 5 to 6 carbonatoms and said ring having alkyl. substituents consisting. of a total ofup to 4 carbon atoms, and R is a .member from the class consisting ofhydrogen, alkyl of-l to 18 carbon atoms, phenyl, naphthyl, phenylalkyl,of up to 18-, carbon atoms, alkylphenylalkyl of up to 30 carbon atoms,alkoxyalkyl of 3 to 24 carbon atoms, hydroxyalkyl ofZ to 12 carbonatoms, and alkylarninoalkyl of 3 to 18 carbon atoms.

2. The compound having the formula l CHaNHz R in which R is alkyl of 1to 18 carbon atoms, R and R taken collectively with the carbon atoms towhich they are joined represent a carbocyclic ring containing 5 to 6carbon atoms, and R and R are alkyl of 1 to 10 carbon atoms.

-4. The compound having the formula R17 -R4 V C gNHzE in which R isalkyl of 1 to 18 carbon atoms, R and R are alkyl of :1 to 10 carbonatoms, and R and R taken collectively with the carbon atoms to whichthey are joined form a carbocyclic ring of to 6 carbon atoms.

5. The compound having the formula in which R is alkyl of 1 to 18 carbonatoms, R is alkyl -of 1.10 l0.carbon atoms, R is alkyl ,of 1 to 4 carbonatoms, and R and R taken collectively with the carbon atom ,towhichtheyare joined form a carbocyclic ring of. 5 to 6 .carbon atoms.

6. The compound-having the formula are hydrogen atoms, R R and R ClNHzit having the formula withsubstantially two. equivalents of hydrogenin the temperature range of about to250 C. inthe presence of ahydrogenation catalyst, in which R taken individually represents amember from the class consisting of alkyl, pheuylalkyl, cycloalkyl,phenyl, naphthyl, and alkylphenyl of up to 10 carbon atoms, R takenindividualy represents a member from the class. consisting of hydrogenand alkyl of 1. to 4 carbon atoms, R and R taken individually representmembers from the class consisting of hydrogen, alkyl, cycloalkyl,phenylalkyl, phenyl, naphthyl, and alkylphenyl of up to 10 carbon atoms,R and R taken collectively with the carbon atoms to which they arejoined form a member from the class consisting of a carbocyclic ring of5 to 6 carbon atoms and said ring having alkyl substituentsconsisting ofa total of up to 4 carbon atoms, R and R taken collectively with thecarbon atoms to which they are joined form a member from the classconsisting of a carbocyclic 'ring of 5 to 6 carbon atoms and said ringhaving alkyl substituents consisting of a total of up to 4 carbon atoms,

R and R taken collectively with thecarbon atoms to -which they arejoined form a member from the class consisting of a carbocyclic ring of5 to 6 carbon atoms and said ring having alkyl substituents consistingof a total of up to 4 carbon atoms, and R is a member from the classconsisting of hydrogen, alkyl of 1 to 18 carbon .atoms, phenyl,naphthyl, phenylalkyl of up to 18 carbon References Cited in the file ofthis patent UNITED STATES PATENTS De Benneville et al. Jan. 1, 1953Prichard July 1, 1958 OTHER REFERENCES Wenkert et al.: I.A.C.S., vol.75, p. 5514 (1953).

1. A MEMBER FROM THE CLASS CONSISTING OF THE COMPOUND HAVING THE FORMULA